Phthalimidoguanidine plant growth regulators

ABSTRACT

Novel compounds are disclosed which have utility as plant growth regulators. Use to produce growth regulators is specifically illustrated. The novel compounds of this invention are phthalimidoguanidines of the following general structural formulas: ##STR1## in which R, R 1  and R 5  are hydrogen or C 1  to C 5  alkyl, R 2  and R 3  are alike or unlike, one of which may be hydrogen but otherwise are substituents selected from C 1  to C 5  alkyl, alkenyl or alkynyl, branches or unbranched, C 2  to C 5  hydroxyalkyl or alkoxyalkyl, C 3  to C 5  cycloalkyl, furfuryl, pyridyl, benzyl, phenyl, C 1  to C 5  alkylphenyl, or --NR 2  R 3  together may be 2,5-dimethyl-1-pyrryl, 4-morpholinyl or 1-pyrrolidinyl, R 4  is halogen, nitro, cyano, trifluoromethyl, C 1  to C 5  alkyl or acyl and n is zero, one or two.

DESCRIPTION OF THE INVENTION

This invention is directed to a novel group of chemical substances which have, to a high degree the ability to change or modify the growth habits of plants. The invention is also directed to methods of regulating growth of plants to obtain desirable modifications, in particular the increase of fruit set, by application to living plants, their seeds, or to the soil of effective amounts of the novel compounds. Also are included methods of manufacturing the compounds, as well as agricultural formulations containing the novel compounds as growth regulators.

Briefly, the novel compounds of this invention are phthalimidoguanidines of the following general structural formulas: ##STR2## in which R, R¹ and R⁵ are hydrogen or C₁ to C₅ alkyl, R₂ and R³ are alike or unlike, one of which may be hydrogen but otherwise are substituents selected from C₁ to C₅ alkyl, alkenyl or alkynyl, branched or unbranched, C₂ to C₅ hydroxyalkyl or alkoxyalkyl, C₃ to C₅ cycloalkyl, furfuryl, pyridyl, benzyl, phenyl, C₁ to C₅ alkylphenyl, or -NR² R³ together may be 2,5-dimethyl-1-pyrryl, 4-morpholinyl or 1-pyrrolidinyl, R⁴ is halogen, nitro, cyano, trifluoromethyl, C₁ to C₅ alkyl or acyl and n is zero, one or two.

Synthesis of the Growth Regulators

The compounds of this invention are readily prepared from the corresponding isothioureido isoindolediones by reaction with amines, as illustrated by the following procedure.

Preparation of 1,1,3-Trimethyl-3-phthalimido-2-phenylguanidine ##STR3##

To a saturated solution of anhydrous dimethylamine in 80 ml. of ethanol was added 4.53 g. (0.01 mol) of 2-(1,2-dimethyl-3-phenylisothioureido)-1H-isoindole-1,3-(2H)-dione, and the resulting solution was heated to 50° C. for 30 minutes. Evaporation and treatment with heptane gave 3.5 g. of crystalline product, m.p. 146°-8° C.

The isothioureido isoindolediones employed as starting materials for the foregoing illustrative procedure may be manufactured by means of the general method comprising reacting a compound of the formula: ##STR4## in a non-reactive polar organic solvent with a compound of the formula R-X in which X is a leaving group exemplified by a chlorine, bromine, iodine or sulfate substituent. Specific procedures which are suitable for synthesis of representative compounds are outlined in the following chart and exemplified below. ##STR5##

It will be understood that when it is desired that R and R¹ shall be different, the alkylation at the sulfur and amino locations is conveniently done in separate reaction steps. The following specific procedures illustrate the general methods of synthesis. All temperatures in the procedures are in °C.

Synthesis of methyl hydrogen phthalate

Methanol (300 ml) was added in a single portion to 148 g (1.00 mole) of phthalic anhydride and the resulting suspension was stirred and heated at reflux for 36 hours; solution occurred during heating. The solvent was removed and the product was recrystallized from a mixture of ethyl acetate and hexane to afford 114.6 g of the title compound (Lit.: Beilstein, 9,797-mp 82.5°, 84°).

Synthesis of methyl phthaloyl chloride

Methyl hydrogen phthalate (110.0 g., 0.611 mole) and thionyl chloride (77.4 g., 0.650 mole) were mixed in 200 ml of chloroform, keeping the temperature below 30°. After stirring for two hours at room temperature, the system was heated at reflux for five hours. The solvent was evaporated at reduced pressure and the crude product (120.9 g) was used without further purification (Lit.: Beilstein, 9, 797-no constants).

Synthesis of 2-(2-carboxybenzoyl)-1-methyl-N-phenylhydrazinethiocarboxamide (I)

This compound was made by reacting phthalic anhydride with 1-methyl-N-phenylhydrazinethiocarboxamide according to conventional procedures, as follows:

The hydrazinethiocarboxamide was dissolved in about 75 ml of dimethylformamide and placed in a 3-necked round-bottomed flask equipped with magnetic stirrer, condenser, additional powder funnel and thermometer. The anhydride was added in portions at 20°. The contents were stirred overnight at room temperature, then poured into ice water the following morning. The resulting solid was recrystallized in hexane and ethanol (m.p. 155°-156° C.).

Optionally ring substituted phthalic anhydrides and substituted 2-carbomethoxybenzoyl chlorides may be condensed with substituted 1-methylhydrazinethiocarboxamides to give desired intermediate compounds as in the following scheme: ##STR6##

These methods are illustrated in the following specific procedures. The identity of the product was confirmed in each instance by means of infrared and nuclear magnetic resonance spectra. All melting points are as determined, uncorrected (Degrees C.).

N-Methyl-N-(phenylthiocarbamoyl)-2-amino-1H-isoindole-1,3-(2H)dione (II)

To an ice-cold solution of 8.25 g (0.025 mole) of 2-(2-carboxybenzoyl)-1-methyl-N-phenylhydrazinethiocarboxamide in 225 ml of 1,2-dimethoxyethane at ˜2° C., a solution of 5.5 g (0.027 mole) of N,N'-dicyclohexylcarbodiimide was added dropwise below 5° C. with stirring. The mixture was stirred in the ice bath and then left at room temperature overnight. The mixture was filtered to remove N,N'-dicyclohexylurea and the filtrate was evaporated below 40° C., under vacuum, to give a yellow amorphous solid which was stirred in 100 ml of dry ether and warmed gently. The ether solution was allowed to stand for a few hours and filtered to give 4.6 g (59%) of whitish yellow crystals, m.p. 142°-144°.

Recrystallization from ethyl acetate-hexane gave whitish crystals, m.p. 151°-153°.

Mass spectrum: M⁺ 311.

N-Methyl-N (phenylthiocarbamoyl)-2-amino-4-methyl-1H-isoindole-1,3-(2H)dione

To a solution of 6.8 g (0.037 mole) of 1-methyl-N-phenylhydrazinethiocarboxamide and 3.0 g of pyridine in 100 ml dry dimethoxyethane, 2-carbomethoxy-6-methylbenzoyl chloride (8.0 g, 0.037 mole) was added and the resulting mixture was stirred at room temperature for 60 hours. The solvent was distilled and the residue was taken up in ethyl acetate, filtered and dried on anhydrous magnesium sulfate. Removal of the solvent gave 10 g (83%) of the desired product, m.p. 110°-115° (dec.).

2-Amino-1H-isoindole-1,3-(2H)dione

To an ice-cold suspension of 14.7 g (0.1 mole) of phthalimide in 100 ml of 95% ethyl alcohol at 5° C., with stirring, 3.6 ml (0.11 mole) of 96.8% hydrazine was added dropwise. A slight exothermic reaction was observed and the mixture was allowed to stir at 5° C. for two hours. The mixture was diluted with 200 ml of ice water, stirred, filtered, washed with water and dried to give 12.2 g (75%) of white powder, m.p. 199°-202°.

Recrystallization from methanol-water gave white needles, m.p. 201°-203°.

N-(Phenylthiocarbamoyl)-2-amino-1H-isoindole-1,3-(2H)dione (III)

To a suspension of 8.2 g (0.05 mole) of 2-amino-1H-isoindole-1,3-(2H)dione in 50 ml of dry 2-propanol, 6 ml (0.05 mole) of phenyl isothiocyanate was added. The mixture was stirred and refluxed for 3 hours, allowed to cool to room temperature and poured into 300 ml of 50% ethyl alcohol. After stirring for one hour, the solid which formed was filtered, washed with water and dried to give 12.1 g (81%) of the desired product as a white powder, m.p. 180°-181°. To make compounds in which Ar is benzoyl, benzoyl isothiocyanates may be employed in procedures of the type described above.

The free base was obtained by suspending the salt in dilute NH₄ OH and extracting with CHCl₃ which was washed with water, then with saturated aqueous NaCl and dried over anhydrous Na₂ SO₄. Removal of the CHCl₃ at reduced pressure in a rotary evaporator gave a residual oil which was crystallized from ether-petroleum ether, wt. 4.6 g, m.p. 90°-91° (75%).

Preparation of 2-(2-Methyl-3-phenylisothioureido)-1H-isoindole-1,3-(2H)-dione (IV)

To 100 ml of dry acetone, 5.0 g (0.018 m) of N-(phenylthiocarbamoyl)-2-amino-1-H-isoindole-1,3-(2H)dione and 2.5 g (0.018 m) powdered anhydrous potassium carbonate was added. To this suspension 1.1 ml (0.018 m) of methyl iodide was added and the mixture was stirred overnight at room temperature. The mixture was poured into ˜300 ml of water, stirred, filtered, washed with water and dried to give 4.4 g (78%) of a yellow powder, m.p. 161°-164°. Mass spectrum: M+311.

Preparation of 2-(1-Allyl-2-methyl-3-phenylisothioureido)-1-H-isoindole-1,3-(2H)dione

To 50 ml of dry acetone, 4.0 g (0.013 m) of the above product (IV), 2.2 g (0.016 m) of powdered anhydrous potassium carbonate, and 1.4 ml (0.016 m) of allyl bromide was added in succession and the mixture stirred overnight at room temperature. The mixture was poured into 300 ml of ice water with stirring. The aqueous layer was decanted and the residue suspended in fresh ice cold water, stirred and filtered to give a yellow semisolid product. This was purified by stirring in hexane to give a yellow powder 1.8 g (39%), m.p. 78°-81°.

Compounds which have been made by means of the foregoing illustrative procedures are listed in Table 1 below.

                                      TABLE 1                                      __________________________________________________________________________     COMPOUNDS OF THE FORMULAS:                                                      ##STR7##                            (1a)                                       ##STR8##                            (1b)                                      No.                                                                               m.p. °C.                                                                     R   R.sup.1                                                                           NR.sup.2 R.sup.3                                                                             (R.sup.4).sub.n                                                                      R.sup.5                                     __________________________________________________________________________     4368                                                                              oil  H   CH.sub.3                                                                          N(C.sub. 2 H.sub.5).sub.2                                                                    n = 0 --                                          4646                                                                              146-8°                                                                       "   "  N(CH.sub.3).sub.2                                                                            "     --                                          4647                                                                              192-5°                                                                       "   "  4-morpholinyl "     --                                          4648                                                                              oil  "   "                                                                  1-piperidyl                                                                       "    --                                                                     4649                                                                              159-61°                                                                      "   "                                                                  1-pyrrolidinyl                                                                    "    --                                                                     4650                                                                              oil  "   "  Nmethyl benzyl                                                                               "     --                                          4651                                                                              oil  "   "  Nisopropyl benzyl                                                                            "     --                                          4652                                                                              oil  "   "  Nmethyl phenyl                                                                               "     --                                          4653                                                                              oil  "   "  Nethyl phenyl "     --                                          4654                                                                              oil  "   "  N(CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                                          "     --                                          4655                                                                              oil  "   "                                                                                  ##STR9##     "     --                                          4656                                                                              oil  "   "  N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                                 "     --                                          4657                                                                              oil  "   "  N propyl phenyl                                                                              "     --                                          4658                                                                              oil  "   "  N(sec.butyl).sub.2                                                                           "     --                                          4659                                                                              oil  "   "  N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                        "     --                                          4660                                                                              oil  "   "  N(allyl).sub.2                                                                               "     --                                          4661                                                                              oil  "   "  N(nonyl).sub.2                                                                               "     --                                          4702                                                                              oil  "   "  N(isobutyl).sub.2                                                                            "     --                                          4703                                                                              oil  "   "  Nmethyl cyclooctyl                                                                           "     --                                          4704                                                                              oil  "   "  N(octyl).sub.2                                                                               "     --                                          4705                                                                              oil  "   "  Nmethyl propyl                                                                               "     --                                          4707                                                                              oil  "   "  Npropyl isopropyl                                                                            "     --                                          4708                                                                              oil  "   "  Npropyl isobutyl                                                                             "     --                                          4709                                                                              oil  "   "  Npropyl sec.butyl                                                                            "     --                                          4710                                                                              oil  "   "  Npropyl butyl "     --                                          4716                                                                              oil  "   "  Nbenzyl 2-propynyl                                                                           "     --                                          4717                                                                              oil  "   "  Nallyl phenyl "     --                                          4718                                                                              oil  "   "  Nethyl p-tolyl                                                                               "     --                                          4719                                                                              233-5°                                                                       "   "  N(CH.sub.3).sub.2                                                                            3-F   --                                          4720                                                                              oil  "   "                                                                  4-morpholinyl                                                                     "    --                                                                     4721                                                                              190-191°                                                                     "   "  NHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                        n = 0 --                                          4722                                                                              136-8°                                                                       "   "  NHallyl       "     --                                          4723                                                                              137-40°                                                                      "   "  NHbenzyl      "     --                                          4724                                                                              154-165°                                                                     "   "  NH(CH.sub.2).sub.3 CH.sub.3                                                                  3-F   --                                          4725                                                                              52-3°                                                                        "   "  NHC(CH.sub.3).sub.3                                                                          n = 0 --                                          4726                                                                              190-191°                                                                     "   "  NHCH.sub.2 CH.sub.2 CH.sub.3                                                                 "     --                                          4727                                                                              185-95°                                                                      "   "  NHcyclopropyl "     --                                          4728                                                                              oil  "   "  NHcyclopentyl "     --                                          4739                                                                              52-4°                                                                        "   "  N(CH.sub.3)(CH.sub.2 CH.sub.2 OH)                                                            "     --                                          4740                                                                              glass                                                                               "   "  N(CH.sub.3).sub.2                                                                            2,5-(CH.sub.3).sub.2                                                                 --                                          4741                                                                              82-5°                                                                        "   "  N(CH.sub.3).sub.2                                                                            4-NO.sub.2                                                                           --                                          4742                                                                              oil  "   "  N(CH.sub.3).sub.2                                                                            4-F   --                                          4743                                                                              148-152°                                                                     "   "  N(CH.sub.3).sub.2                                                                            4-CN  --                                          4756                                                                              103-5°                                                                       "   "  N(CH.sub.3).sub.2                                                                            4-CF.sub.3                                                                           --                                          4757                                                                              137-9°                                                                       "   "  N(CH.sub.3).sub.2                                                                            2,4-Cl.sub.2                                                                         --                                          4758                                                                              glass                                                                               "   "  N(CH.sub.3).sub.2                                                                            3-COCH.sub.3                                                                         --                                          4759                                                                              glass                                                                               "   -- N(CH.sub.3).sub.2                                                                            n = 0 C.sub.2 H.sub.5                             4760                                                                              glass                                                                               "   -- N(CH.sub.3).sub.2                                                                            n = 0 CH.sub.3                                    4762                                                                              164-72°                                                                      "   H  N(CH.sub.3).sub.2                                                                            3-F   --                                          4764                                                                              oil  "   CH.sub.3                                                                          1-pyrrolidinyl                                                                               "     --                                          4850                                                                              oil  4-CH.sub.3                                                                         CH.sub.3                                                                          NH(CH.sub.2).sub.3 CH.sub.3                                                                  n = 0 --                                          4956                                                                              oil  H   "  NHCH.sub.2 CH.sub.2 OCH.sub.3                                                                "     --                                          4957                                                                              oil  "   "  Nmethyl furfuryl                                                                             "     --                                          4958                                                                              oil  "   "                                                                  2,5-dimethyl-l-pyrryl                                                             "    --                                                                     4959                                                                              oil  "   "  NH2-pyridyl   "     --                                          __________________________________________________________________________

Use of the Growth Regulators

In highly active compounds, phytotoxic and growth-altering effects of pre-emergent and post-emergent application are often readily apparent. These effects may be demonstrated by means of the following illustrative procedures.

Pre-emergent Application

Disposable paper trays about 2 1.2 inches deep were filled with soil and sprayed with aqueous spray mixtures at a rate of 5 lb. of active chemical per acre of sprayed area, were seeded with 6 species of plant seeds and were then covered with about 1/4 inch of soil. The spray mixtures were prepared by dissolving the proper amount of growth regulant compound in 15 ml. of acetone, adding 4 ml. of a solvent-emulsifier consisting of 60 wt. percent of a commercial polyoxyethylated vegetable oil emulsifier (96 wt. percent active ingredient, Emulphor EL-719), 20 wt. percent xylene and 20 wt. percent deodorized kerosene, then bringing total volume up to 60 ml. by addition of warm water. Twenty-one days after seeding and treatment the plantings were examined and plant injury was rated according to the following schedule.

DEGREE OF EFFECT

0=no effect,

1=slight effect, plants recovered,

2=moderate effect, injury to 26 to 75 percent,

3=severe effect, injury to 76 to 99 percent, of foliage,

4=maximum effect (all plants died).

Post-emergent Application

Several species of plants were grown in potting soil in disposable styrofoam trays and tomatoes were grown in four-inch pots in the greenhouse. Aqueous spray formulations were prepared and the growing plants were sprayed at a spray volume of 60 gallons per acre and an application rate of 5 lb. per acre. Spray mixtures were prepared in the manner described above. For comparative purposes, plants were also sprayed at 60 gal./acre with a spray mixture containing no growth regulant. Plant injury was again rated according to the schedule disclosed above.

Observations of growth regulant effects in both pre- and post-emergent tests were observed and recorded as follows:

    ______________________________________                                         Effect            Abbreviation in Tables                                       ______________________________________                                         Formative effect on new growth                                                                   F                                                            Epinasty          E                                                            Growth reduction  G                                                            Necrosis          N                                                            Non-emergence     K                                                            Chlorosis         C                                                            ______________________________________                                    

In the table below there are tabulated the observations of pre- and post-emergent herbicidal and growth regulator effects resulting from use of one of the growth regulators of this invention according to the procedures set forth above.

                                      TABLE 2                                      __________________________________________________________________________     EFFECTS OF THE COMPOUNDS ON PLANT SPECIES                                      Pre-emergent Effects              Post-emergent Effects                        Compound                                                                             Digitaria                                                                            Celosia                                                                             Bromus                                                                             Setaria                                                                            Raphanus                                                                            Beta                                                                               Setaria                                                                            Medicago                                                                            Avena                                                                              Raphanus                                                                            Beta                                                                               Lycopersicum           No.   sanguinalis                                                                          plumosa                                                                             inermis                                                                            italica                                                                            sativus                                                                             vulgaris                                                                           italica                                                                            sativa                                                                              sativa                                                                             sativus                                                                             vulgaris                                                                           esculentum             __________________________________________________________________________     4368  F3G3  K4   F3G3                                                                               F3G3                                                                               F3G3 F3G3                                                                               F1G1                                                                               F3G2 F2G1                                                                               G1   F3G2                                                                               F3G1                                                                  N2F1                            __________________________________________________________________________

Post-emergent Application at Lower Rates on 24 Species

Twenty-four species of plants were grown in potting soil in disposable styrofoam trays and tomatoes were grown in four-inch pots in the greenhouse. Aqueous spray formulations were prepared and the growing plants were sprayed at a spray volume of 40 gallons per acre and application rates of 3 lb. and 1 lb. per acre. The spray mixtures were prepared by dissolving the proper amount of growth regulator compound in 15 ml of acetone, adding 4 ml of a solvent-emulsifier mixture consisting of 60 wt. percent of a commercial polyoxyethylated vegetable oil emulsifier (96 wt. percent active ingredient, Emulphor EL-719), 20 wt. percent xylene and 20 wt. percent deodorized kerosene, then bringing total volume up to 80 ml by addition of warm water. Of this spray mixture, a 50 ml portion was used to spray the plants at a rate of 3 lb. per acre of sprayed area. The remaining 30 ml. was diluted to 90 ml. with warm water and was used to spray the plants at a rate of 1 lb. per acre. One large, more mature tomato plants was included in the test along with the other, smaller growing plants. For comparative purposes, plants were also sprayed at a spray volume of 40 gallons per acre with a spray mixture containing no growth regulator.

Approximately fifteen days after spraying, the plants were observed and the results were evaluated according to the schedule disclosed above. Results obtained with representative compounds are presented in Table 3. The test species are as follows:

    ______________________________________                                                  Common         Scientific                                             Number   Name           Name                                                   ______________________________________                                         I        Pigweed        Amaranthus retroflexus                                 II       Lambsquarters  Chenopodium album                                      III      Crabgrass      Digitaria sanguinalis                                  IV       Downey brome   Bromus tectorum                                        V        Giant foxtail  Setaria faberii                                        VI       Nutsedge       Cyperus esculentus                                     VII      Peanuts        Arachis hypogaea                                       VIII     Cotton         Gossypium herbaceum                                    IX       Tomato         Lycopersicum esculentum                                X        Sugar beets    Beta vulgaris                                          XI       Wild buckwheat Polygonum convolvulus                                  XII      Wild mustard   Brassica kaber                                         XIII     Mature tomato plant                                                                           Lycopersicum esculentum                                XIV      Cocklebur      Xanthium pensylvanicum                                 XV       Morning glory  Ipomea purpurea                                        XVI      Soybeans       Soja max                                               XVII     Barnyard grass Echinochloa crusgalli                                  XVIII    Green foxtail  Setaria viridis                                        XIX      Alfalfa        Medicago sativa                                        XX       Corn           Zea mays                                               XXI      Grain sorghum  Sorghum vulgare                                        XXII     Shattercane    Sorghum bicolor                                        XXIII    Wheat          Triticum aestivum                                      XXIV     Wild oats      Avena fatua                                            XXV      Rice           Oryza sativa.                                          ______________________________________                                    

                                      TABLE 3                                      __________________________________________________________________________     POST-EMERGENT EFFECTS ON 24 SPECIES                                            __________________________________________________________________________     Appl'n.                                                                        Rate      Compound Nos.                                                        Species                                                                              (lb/A)                                                                             4646 4677 4648 4649 4650                                                                               4651                                         __________________________________________________________________________     I     3   F2G2 F3G3 F3G3 F3G3 F3G3                                                                               F3G3                                               1   F1   F3G3 F3G3 F3G2 F3G3                                                                               F3G3                                         II    3   F2G2 F3G3 F3G3 F3G3 F3G3                                                                               F3G3                                               1   F1   F2G2 F3G3 F1G1 F3G3                                                                               F3G3                                         III   3   0    F1   F2G2 G1   F3G3                                                                               F2G1                                               1   0    0    F1G1 0    F1  F2G1                                         IV    3   0    0    F1   0    F1G1                                                                               0                                                  1   0    0    0    0    0   0                                            V     3   0    F1   F3G3 F1   F3G3                                                                               F1G1                                               1   0    0    F2G2 0    F1  F1G1                                         VI    3   0    0    0    0    F1  0                                                  1   0    0    0    0    0   0                                            VII   3   0    0    0    0    F1  F1                                                 1   0    0    0    0    0   0                                            VIII  3   0    F2   F1   F2G2 F3G3                                                                               F3G1                                               1   0    F1   F1   F1   F2G1                                                                               F2G1                                         IX    3   F2   G2F3 F3G3 F3G3 F3G3                                                                               F3G3                                               1   F1   F3   F3G3 F3   F3G2                                                                               F3G2                                         X     3   F2   F1G1 F3G3 F2G2 F3G3                                                                               F3G3                                               1   F1   F1   F3G3 F1   F2G1                                                                               F2G1                                         XI    3   0    0    F2G2 F1G1 F2G2                                                                               F3G2                                               1   0    0    F2G1 0    F1  F1                                           XII   3   F1   F1   F3G2 F1   F2G2                                                                               F3G3                                               1   0    0    F3G2 0    F1  C2F1                                         XIII  3   F1   F2   F3   F3   F3G1                                                                               F3                                                 1   F1   F2   F3   F2   F3  F3                                           XIV   3   F1   0    F2G1 F1   F2G2                                                                               F2                                                 1   0    0    F1   0    F2G1                                                                               F1                                           XV    3   F1   F2   F2G2 --   F3G3                                                                               F3G2                                               1   0    F1   F1G1 0    F2G2                                                                               F2G1                                         XVI   3   F2   G2F2 F3G3 F2   F3G3                                                                               F3G3                                               1   F1   F2G1 F3G3 F1   F3G3                                                                               F3G2                                         XVII  3   0    0    F1   0    F1G1                                                                               F1                                                 1   0    0    F1   0    F1  0                                            XVIII 3   0    F1   F2G1 F1   F2G2                                                                               F2G2                                               1   0    0    F1   0    F1G1                                                                               F1G1                                         XIX   3   F1   F2   F3G3 F2   F3G3                                                                               F3G3                                               1   0    F1   F3G2 F1   F3G2                                                                               F3G1                                         XX    3   0    0    C1   0    F1  0                                                  1   0    0    0    0    0   0                                            XXI   3   0    F1   F1   0    F2  F2                                                 1   0    0    0    0    F1  F1                                           XXII  3   0    F1   F1   0    F2  F2                                                 1   0    0    0    0    0   F1                                           XXIII 3   0    F1   0    0    F1  F1                                                 1   0    0    0    0    0   F1                                           XXIV  3   0    0    0    0    F1  F1                                                 1   0    0    0    0    0   0                                            XXV   3   0    0    0    0    F1  F1                                                 1   0    0    0    0    0   0                                            Comments  increased                                                                           increased                                                                           more more more                                                                               more                                                   fruit set                                                                           fruit set                                                                           fruit                                                                               fruit                                                                               fruit                                                                              fruit                                                            set  set  set,                                                                               set,                                                                       tillers                                                                            tillers                                      __________________________________________________________________________     Appl'n.                                                                        Rate      Compound Nos.                                                        Species                                                                              (lb/A)                                                                             4652 4653 4654 4655 4656                                                                               4657                                         __________________________________________________________________________     I     3   F3G3 F3G3 F3G3 F3G3 F3G3                                                                               F3G3                                               1   F3G3 F3G3 F3G3 F3G3 F3G3                                                                               F3G3                                         II    3   F3G3 F3G3 F3G3 F3G3 F3G3                                                                               F3G3                                               1   F3G3 F3G3 F3G3 F3G2 F3G3                                                                               F3G3                                         III   3   F3G2 F3G2 F1   G1F1 F2G1                                                                               F1G1                                               1   F1G1 F1   F1   F1   F1G1                                                                               F1                                           IV    3   F1   F1   0    0    F1  0                                                  1   0    0    0    0    0   0                                            V     3   F2   F3G2 F2G1 F2G1 F2G2                                                                               F2G2                                               1   F2   F2G1 F2   F2G1 F1  F1                                           VI    3   0    0    0    0    0   0                                                  1   0    0    0    0    0   0                                            VII   3   F1   F1   F1   0    F1  F1                                                 1   0    0    0    0    0   0                                            VIII  3   F2G1 F2G1 F2   F1   F3G3                                                                               F2G1                                               1   F2   F2   F2   F1   F2  F1                                           IX    3   F3G3 F3G3 F3G3 F3G3 F3G3                                                                               F3G3                                               1   F3G3 F3G3 F3G3 F3G2 F3G3                                                                               F3G3                                         X     3   F3G3 F3G2 F3G2 F3G3 F3G3                                                                               F3G3                                               1   F3G2 F3G2 F3G2 F3G2 F2G2                                                                               F2G2                                         XI    3   F2G2 F2G2 F2G2 F2G2 F2G2                                                                               F2G2                                               1   F1G1 F1   F2   F1   F1G1                                                                               F1                                           XII   3   F2G2 F3G2 F2G2 F3G2 F2G2                                                                               F2G1                                               1   C2F1 C2F1 F2G1 C1F1 F1C2                                                                               F1C1                                         XIII  3   F3G2 F3G3 F3G3 F3G3 F3G3                                                                               F3G3                                               1   F3   F3G2 F3G1 F3G2 F3G2                                                                               F3G3                                         XIV   3   F2G1 F2G1 F2G1 F2G1 F2G1                                                                               F3G2                                               1   F1   F1   --   F1   F1G1                                                                               F1                                           XV    3   F3G2 F3G3 F3G3 F3G3 F3G3                                                                               F3G3                                               1   F3G2 G2F2 F2G1 F2G2 F3G2                                                                               F2G1                                         XVI   3   F3G3 F3G3 F3G3 F3G3 F3G3                                                                               F3G3                                               1   F3G2 F3G2 F3G2 F3G2 F3G3                                                                           F3G2                                             XVII  3   F2G1 F2G1 F1G1 F1   F1  F1                                                 1   F1   F1   0    0    0   0                                            XVIII 3   F2G2 F3G2 F2G2 F2G2 F2G2                                                                               F2G2                                               1   F2G2 F3G2 F2G2 F2G1 F1G1                                                                               F2G1                                         XIX   3   F3G3 F3G3 F3G2 F3G3 F3G3                                                                               F3G3                                               1   F3G2 F3G2 F3G1 F3G1 F3G2                                                                               F3G1                                         XX    3   F1   F2G1 F1   F1   F1G1                                                                               F1                                                 1   0    F1   0    0    0   0                                            XXI   3   F3G1 F3G2 F2G1 F1   F2G1                                                                               F2G1                                               1   F1   F1   F1   F1   0   F1                                           XXII  3   F3G1 F3G2 F2G1 F1   F2G1                                                                               F2G1                                               1   F1   F1   F1   F1   F1  F1                                           XXIII 3   F2G1 F1G1 F1   0    F1  F1                                                 1   0    0    0    0    0   0                                            XXIV  3   F1G1 F1   F1   0    F1  F1                                                 1   0    0    0    0    0   0                                            XXV   3   F1G1 F1   F1   0    F1  F1                                                 1   0    0    0    0    0   0                                            Comments  more more more      more                                                       fruit                                                                               tillers                                                                             tillers   tillers                                                    set                                                                  __________________________________________________________________________     Appl'n.                                                                        Rate      Compound Nos.                                                        Species                                                                              (lb/A)                                                                             4658 4659 4660 4661 4702                                                                               4703                                         __________________________________________________________________________     I     3   F3G3 F3G3 F3G3 F3G3 C3G3                                                                               F1                                                 1   F3G3 F3G3 F3G2 F3G3 F3G2                                                                               F1                                           II    3   F3G3 F3G3 F3G3 F3G3 C3G3                                                                               F1                                                 1   F3G3 F3G3 F3G2 F3G3 F3G3                                                                               F1                                           III   3   F2G2 F1G1 G2F1 F3G2 G2F2                                                                               0                                                  1   F1G1 F1   G1   F2G1 F1  0                                            IV    3   F1   0    G1   G1   G1  0                                                  1   0    0    0    0    0   0                                            V     3   F2G2 F1   F2G2 F3G2 F3G2                                                                               0                                                  1   F1   0    F1   F2G1 F1  0                                            VI    3   0    0    0    0    0   0                                                  1   0    0    0    0    0   0                                            VII   3   F1   0    F1   F1   0   0                                                  1   0    0    0    0    0   0                                            VIII  3   F2G1 F2G1 F3G3 F2G1 F1  0                                                  1   F1   F1   F1   F1   0   0                                            IX    3   F3G3 F3G3 F3G3 F3G3 F3G3                                                                               F2                                                 1   F3G3 F3G3 F3G3 F3G3 F3G1                                                                               F2                                           X     3   F3G2 F3G3 F3G2 F3G3 F3G2                                                                               F1                                                 1   F3G2 F3G2 F3G2 F3G2 F2  F1                                           XI    3   F2G2 F2G1 F1G1 F1G1 F1  0                                                  1   F1G1 F1   F1   F1   0   0                                            XII   3   F2G2 F2G1 F3G2 F3G3 C2F1                                                                               0                                                  1   F1C1 F1   G1F1 F1G1 0   0                                            XIII  3   F3G3 F3G3 F3G3 F3G3 F3G1                                                                               F3                                                 1   F3G3 F3G2 F3   F3   F3  F2                                           XIV   3   F2G2 F2G1 F2G1 F2   F1  F1                                                 1   F1   F1   F2   F1   F1  F1                                           XV    3   F3G3 F3G3 F3G2 F3G3 F3G2                                                                               F2G2                                               1   F3G3 F3G3 F3G1 F3G2 F1  F1                                           XVI   3   F3G3 F3G3 F3G3 F3G3 F3G2                                                                               F3G2                                               1   F3G3 F3G2 F3G3 F3G3 F3G2                                                                               F2G2                                         XVII  3   F1   F1   F1   F1   0   0                                                  1   0    0    0    0    0   0                                            XVIII 3   F2G2 F2G2 F2G1 F2G2 F2G1                                                                               0                                                  1   F2G1 F1   F1G1 F1   F1  0                                            XIX   3   F3G3 F3G3 F3G2 F3G3 F3G2                                                                               F2C1                                               1   F3G2 F3G1 F3G2 F3G1 C1F2                                                                               F1                                           XX    3   F1   F1   F1   F1   F1  0                                                  1   F1   0    0    0    0   0                                            XXI   3   F2G1 F2   F2G1 F2G1 F2  F1                                                 1   F2   0    F1   F1   F1  0                                            XXII  3   F2G1 F2   F2G1 F2G1 F2  F1                                                 1   F2   0    F1   F1   F1  0                                            XXIII 3   F1   F1   F1   F1   F1  0                                                  1   F1   0    0    0    0   0                                            XXIV  3   F1   F1   F1   0    F1  0                                                  1   0    0    0    0    0   0                                            XXV   3   F1   0    F1   F1   F1  0                                                  1   0    0    0    0    0   0                                            Comments  more more more more more                                                                               more                                                   tillers                                                                             fruit                                                                               fruit                                                                               fruit                                                                               fruit                                                                              fruit                                                       set  set, set, set,                                                                               set                                                              tillers                                                                             tillers                                                                             tillers                                          __________________________________________________________________________     Appl'n.                                                                        Rate      Compound Nos.                                                        Species                                                                              (lb/A)                                                                             4704                                                                               4705                                                                               4707 4708 4709 4710                                          __________________________________________________________________________     I     3   F3G3                                                                               F3G3                                                                               F3G3 F3G3 F3G3 F3G3                                                1   F3G2                                                                               F3G3                                                                               F3G3 F3G3 F3G3 F3G3                                          II    3   F3G3                                                                               F3G3                                                                               F3G3 F3G3 F3G3 F3G3                                                1   F3G2                                                                               F3G3                                                                               F3G3 F3G3 F3G3 F3G3                                          III   3   F1  F2G1                                                                               F3G2 F3G2 F3G2 F3G3                                                1   0   0   F1G1 F1G1 F1G1 F1G1                                          IV    3   G1  G1  G1   G1   G1   G1                                                  1   0   0   0    0    0    0                                             V     3   F1G1                                                                               F2G2                                                                               F2G2 F2G2 F3G2 F3G2                                                1   0   F1  F1   F2G1 F1   F2                                            VI    3   0   0   0    0    0    0                                                   1   0   0   0    0    0    0                                             VII   3   0   0   F1   0    F1   F1                                                  1   0   0   0    0    0    0                                             VIII  3   N3G2                                                                               F1  F2G1 F2   F2   F2G1                                                1   NqF1                                                                               F1  F2   F1   F1   F1                                            IX    3   N4  F3G3                                                                               F3G3 F3G3 F3G3 F3G3                                                1   F3G2                                                                               F3G2                                                                               F3G2 F3G2 F3G2 F3G2                                          X     3   F3G3                                                                               F3G3                                                                               F3G3 F3G3 C3F3G3                                                                              F3G3C3                                              1   F2G2                                                                               F3G2                                                                               F3C2 F3G2C2                                                                              F2G2C2                                                                              F3G2C2                                        XI    3   F1  F1  F1   F1   F2G1 F2G1                                                1   0   0   0    0    0    F1                                            XII   3   N4  C3F2                                                                               C3G3 C3G2 C3G3 C3G3                                                1   N2F2                                                                               F1C1                                                                               C2F1 C2F1 C2F1 C2F1                                          XIII  3   N3F3                                                                               F3G2                                                                               F3G2 F3   F3C1 F3G1                                                1   N2F2                                                                               F3  F3   F3   F3   F3                                            XIV   3   F1N1                                                                               --  --   F1   F1   --                                                  1   F1  F2  F1   F1   F1   F1                                            XV    3   F3G3                                                                               F2G2                                                                               F3G3 F3G2 F3G3 F3G3                                                1   F2  F2G2                                                                               F2   F2G1 F2G1 F2G2                                          XVI   3   F3G3                                                                               F3G3                                                                               F3G3 F3G3 F3G3 F3G3                                                1   F3G2                                                                               F3G3                                                                               F3G3 F3G3 F3G3 F3G3                                          XVII  3   0   F1G1                                                                               F2G1 F1   F2G1 F2G1                                                1   0   0   0    0    F1   F1                                            XVIII 3   F2G1                                                                               F2G2                                                                               F2G2 F3G2 F2G2 F2G2                                                1   F1  F1  F1   F1   F1G1 F1                                            XIX   3   F3G3                                                                               F3G2                                                                               F3G3 F3G3 F3G3 F3G3                                                1   F1N1                                                                               F3G1                                                                               F3G1 F2G1 F2G1 F3G2                                          XX    3   F1  F1  F1   F1   F1   F2G1                                                1   0   0   F1   F1   0    F1                                            XXI   3   F3G2                                                                               F2G1                                                                               F2G1 F2G1 F2G1 F3G2                                                1   F1  F1  F1   F1   F1   F2                                            XXII  3   F3G2                                                                               F2G1                                                                               F2G1 F2G2 F2G1 F3G2                                                1   F1  F1  F2   F2   F1   F2                                            XXIII 3   N1G1                                                                               F1  F1   F1   F1   F1                                                  1   0   0   F1   F1   0    0                                             XXIV  3   N1G1                                                                               F1  F1   F1   F1   F2                                                  1   0   F1  F1   F1   F1   F1                                            XXV   3   N1G1                                                                               F2  F1   F1   F1   C1F1                                                1   0   0   F1   0    0    0                                             Comments  more                                                                               more                                                                               more more more more                                                    fruit                                                                              fruit                                                                              fruit                                                                               fruit                                                                               fruit                                                                               fruit                                                   set set,                                                                               set, set, set, set,                                                        tillers                                                                            tillers                                                                             tillers                                                                             tillers                                                                             tillers                                       __________________________________________________________________________     Appl'n.                                                                        Rate      Compound Nos.                                                        Species                                                                              (lb/A)                                                                             4716 4717 4718 4719                                                                               4720 4721                                         __________________________________________________________________________     I     3   F3G3 F3G3 F3G3 F1  F3G3 F1                                                 1   F3G3 F3G3 F3G3 0   F3G2 0                                            II    3   F3G3 F3G3 F3G3 F1  F3G3 F1                                                 1   F3G3 F3G2 F3G3 0   F3G3 0                                            III   3   F2G1 F2G1 F1G1 0   F2G1 0                                                  1   F1   F1   F1   0   F1G1 0                                            IV    3   F1   0    0    0   0    0                                                  1   0    0    0    0   0    0                                            V     3   F3G2 F3G2 F2G1 0   F2G2 0                                                  1   F1   F1   F1   0   F1   0                                            VI    3   0    0    0    0   0    0                                                  1   0    0    0    0   0    0                                            VII   3   F1   F1   0    0   F1   0                                                  1   0    0    0    0   0    0                                            VIII  3   F1   F2   F1   0   F2   0                                                  1   F1   0    F1   0   F1   0                                            IX    3   F3G3 F3G3 F3G3 F1  F3G3 F1                                                 1   F3G2 F3G1 F3G3 F1  F3G2 F1                                           X     3   F3G3 F3G3 F3G3C2                                                                              F1  F3G3C3                                                                              F1                                                 1   F2G2C1                                                                              F2G1 F3C2 0   F2G2C1                                                                              F1                                           XI    3   F1G1 F2G2 F2G1 0   F1G1 0                                                  1   F1   F1   F1   0   F1   0                                            XII   3   F1G1 C1F2G2                                                                              F2C2 0   F3C3G2                                                                              0                                                  1   F1C1 F1C1 F1C1 0   F2C2G1                                                                              0                                            XIII  3   F3G1 F3G1 F3G1 F1  F3   F1                                                 1   F3   F3   F3   0   F2   0                                            XIV   3   F1   F2   --   0   --   0                                                  1   F1   F1   F1   0   F1   0                                            XV    3   F2G2 F3G3 F3G2 0   F3G2 0                                                  1   F2G1 F2G1 F2G2 0   F2G1 0                                            XVI   3   F3G3 F3G3 F3G3 0   F3G3 F1                                                 1   F3G3 F3G3 F3G3 0   F3G3 0                                                  3   F1   F1   F1   0   F2G1 0                                                  1   0    0    0    0   0    0                                            XVIII 3   F1   F2G1 F1G1 0   F3G2 0                                                  1   F1   F1   F1   0   F2G1 0                                            XIX   3   F3G2 F3G1 F3G2 F1  F3G3C1                                                                              F1                                                 1   F3   F2C1 F2C1 0   F3C1 0                                            XX    3   F1   F1   F1   0   F1   0                                                  1   0    0    0    0   F1   0                                            XXI   3   F2   F2   F2   0   F2G1 0                                                  1   F1   F1   F1   0   F1   0                                            XXII  3   F2   F2   F2   0   F2G1 0                                                  1   F1   F1   F1   0   F1   0                                            XXIII 3   0    0    0    0   F2G1 0                                                  1   0    0    0    0   0    0                                            XXIV  3   F1   F1   F1   0   F1   0                                                  1   F1   F1   F1   0   F1   0                                            XXV   3   F1   F1   F2   0   F1G1C1                                                                              0                                                  1   0    0    F1   0   0    0                                            Comments  more more more more                                                                               more more                                                   fruit                                                                               fruit                                                                               fruit                                                                               fruit                                                                              fruit                                                                               fruit                                                  set, set, set, set set, set                                                    tillers                                                                             tillers                                                                             tillers  tillers                                           __________________________________________________________________________     Appl'n.                                                                        Rate      Compound Nos.                                                        Species                                                                              (lb/A)                                                                             4722 4723 4724 4725 4726                                                                               4727                                         __________________________________________________________________________     I     3   F1   F1G1 F3G3 F3G3 0   F3G2                                               1   0    0    F1   F3G3 0   G1                                           II    3   F1   0    F3G3 F3G3 0   F1G1                                               1   F1   0    F2G1 F3G3 0   0                                            III   3   0    0    0    F2G2 0   0                                                  1   0    0    0    F1G1 0   0                                            IV    3   0    0    0    G1   0   0                                                  1   0    0    0    0    0   0                                            V     3   0    0    0    F2G2 0   0                                                  1   0    0    0    F1   0   0                                            VI    3   0    0    0    0    0   0                                                  1   0    0    0    0    0   0                                            VII   3   0    0    0    0    0   0                                                  1   0    0    0    0    0   0                                            VIII  3   0    0    0    F1   F1  N1                                                 1   0    0    0    0    0   0                                            IX    3   G1F2 F2G2 F3G3 F3G3 F2G1                                                                               F3G3                                               1   F1   F1   F3G2 F3G3 F1  F3G1                                         X     3   F2   F1   F3G3C1                                                                              F3G3C2                                                                              F1C1                                                                               F2G2                                               1   F1   F1   F2G1 F2G2C1                                                                              0   F2                                           XI    3   0    0    F1   F2G2 0   0                                                  1   0    0    0    F1   0   0                                            XII   3   0    0    F1   F3G2C2                                                                              0   F1                                                 1   0    0    0    F1C1 0   0                                            XIII  3   F3   F2   F3   F3G3 F1  F3                                                 1   F2   F2   F3   F3G2 F1  F2                                           XIV   3   0    0    F1   F2   0   0                                                  1   0    0    0    F1   0   0                                            XV    3   F1   0    F2G1 F2G2 0   F1                                                 1   0    0    F1   F2G1 0   0                                            XVI   3   F1   0    F2G2 F3G3 F1  N1F2                                               1   0    0    F2   F3G2 0   N1                                           XVII  3   0    0    0    F1   0   0                                                  1   0    0    0    0    0   0                                            XVIII 3   0    0    F1   F3G2 0   0                                                  1   0    0    0    F2G1 0   0                                            XIX   3   F1   F1   F3G2 F3G3 F1  F2                                                 1   0    F1   F2   F3G2 0   F1                                           XX    3   0    0    0    F1   0   0                                                  1   0    0    0    0    0   0                                            XXI   3   0    0    0    F2G1 0   0                                                  1   0    0    0    F2   0   0                                            XXII  3   0    0    0    F2G1 0   0                                                  1   0    0    0    F2   0   0                                            XXIII 3   0    0    0    0    0   0                                                  1   0    0    0    0    0   0                                            XXIV  3   0    0    0    F1   0   0                                                  1   0    0    0    0    0   0                                            XXV   3   0    0    0    0    0   0                                                  1   0    0    0    0    0   0                                            Comments  more more      more more                                                       fruit                                                                               fruit     fruit                                                                               fruit                                                      set  set       set  set                                              __________________________________________________________________________     Appl'n.                                                                        Rate      Compound Nos.                                                        Species                                                                              (lb/A)                                                                             4728 4739 4740 4741 4742                                                                               4743                                         __________________________________________________________________________     I     3   F3G3 F3G3 F3G2 F1G1 F3G3                                                                               F3G3                                               1   G3F3 F3G3 F2G2 F1G1 F3G2                                                                               F1G1                                         II    3   F3G3 F3G3 F3G2 F1G1 F3G3                                                                               F3G3                                               1   F3G2 F3G3 F2B2 F1   F1G1                                                                               F1G1                                         III   3   F2G2 F2G1 0    0    F2G2                                                                               0                                                  1   F1   F1   0    0    0   0                                            IV    3   F3G2 0    0    0    0   0                                                  1   F2G2 0    0    0    0   0                                            V     3   F2G2 F2G2 0    0    0   0                                                  1   0    F1   0    0    0   0                                            VI    3   0    C1   0    0    0   0                                                  1   0    0    0    0    0   0                                            VII   3   0    F1   0    0    0   0                                                  1   0    0    0    0    0   0                                            VIII  3   0    F1   0    0    0   0                                                  1   0    0    0    0    0   0                                            IX    3   F3G3 F3G3 F2G1 G1F2 F3G3                                                                               F3G2                                               1   F3G3 F3G3 F1   F2G1 F3G3                                                                               F2G1                                         X     3   F3G3C2                                                                              F3G2C2                                                                              F2   F2   F3G2                                                                               F1                                                 1   F3G1 F2G2 F1   F1   F2G1                                                                               F1                                           XI    3   F1   F1   F1   0    0   0                                                  1   0    F1   0    0    0   0                                            XII   3   F2G2C1                                                                              F1G1 C1   0    F1  F1                                                 1   F1C1 F1C1 0    0    0   0                                            XIII  3   F3G3 F3G1 F3   F2   F3  F3                                                 1   F3G3 F3   F1   F1   F3  F2                                           XIV   3   F2   F1   0    0    0   0                                                  1   F1   0    0    0    0   0                                            XV    3   F3G3 F2G2 N2F1 N3F2 N3G3                                                                               N1                                                 1   F3G2 F2G1 0    N1   N1G1                                                                               0                                            XVI   3   F3G3 F3G3 F1   F1   F3G3                                                                               F1                                                 1   F3G3 F3G3 0    0    F2  0                                            XVII  3   F1   F1   0    0    0   0                                                  1   0    F1   0    0    0   0                                            XVIII 3   F2G2 F2G2 0    0    0   0                                                  1   F1G1 F1   0    0    0   0                                            XIX   3   F3G3 F3G3 F1   F1   F3G1                                                                               C1F1                                               1   F3G3C2                                                                              F3G2 F1   0    F2  C1F1                                         XX    3   C1   F1   0    0    0   0                                                  1   0    0    0    0    0   0                                            XXI   3   F2G1 F2   0    0    0   0                                                  1   F1   F1   0    0    0   0                                            XXII  3   F2G1 F2   0    0    0   0                                                  1   F1   F1   0    0    0   0                                            XXIII 3   0    G1   0    0    0   0                                                  1   0    0    0    0    0   0                                            XXIV  3   F1   F1   0    0    0   0                                                  1   0    0    0    0    0   0                                            XXV   3   0    F1C1 0    0    0   0                                                  1   0    F0   0    0    0   0                                            Comments  more more more more more                                                                               more                                                   fruit                                                                               fruit                                                                               fruit                                                                               fruit                                                                               fruit                                                                              fruit                                                  set  set  set  set  set set                                          __________________________________________________________________________     Appl'n.                                                                        Rate      Compound Nos.                                                        Species                                                                              (lb/A)                                                                             4756                                                                               4758                                                                               4759                                                                              4760                                                                               4762                                                                               4764 4850                                         __________________________________________________________________________     I     3   F3G3                                                                               F1G1                                                                               0  0   F3G2                                                                               F3G3 F3G3                                               1   F2G1                                                                               0   0  0   F2G1                                                                               F3G2 F3G3                                         II    3   F3G3                                                                               F1G1                                                                               F1 0   F2G2                                                                               F3G3 F3G3                                               1   F2  0   0  0   F1  F3G3 F3G2                                         III   3   0   0   0  0   0   F1G1 0                                                  1   0   0   0  0   0   0    0                                            IV    3   0   0   0  0   0   0    0                                                  1   0   0   0  0   0   0    0                                            V     3   F1  0   0  0   0   F2G1 0                                                  1   0   0   0  0   0   C1   0                                            VI    3   0   0   0  0   0   0    0                                                  1   0   0   0  0   0   0    0                                            VII   3   0   0   0  0   0   F1   0                                                  1   0   0   0  0   0   F1   0                                            VIII  3   F2  N1  0  0   F1  F2G1 N1                                                 1   F1  0   0  0   0   F2   0                                            IX    3   F3G3                                                                               F2G2                                                                               0  0   F1  F3G3 F3G3                                               1   F2  F2  0  0   F1  F3G2 F3                                           X     3   F2  F1  F1 F1  F1  F3G3C3                                                                              F2G1                                               1   F2  0   0  F1  F1  F2G2 F2                                           XI    3   F1G1                                                                               0   0  0   0   F1C1 F1                                                 1   0   0   0  0   0   F1   0                                            XII   3   F2  0   G1 0   0   F3G2C2                                                                              --                                                 1   0   0   0  0   0   F1C1 F1G1                                         XIII  3   F3  F3  N1 N1F1                                                                               F1  F3C2 F3G1                                               1   F2  F2  0  0   0   F3   F3                                           XIV   3   F2  0   0  0   0   F2G1 F1                                                 1   0   0   0  0   0   F1   F1                                           XV    3   F2  N1  0  0   F1  F3G2 F2G1                                               1   F1  0   0  0   0   F2G1 F2                                           XVI   3   F2  N1F1                                                                               N1 F1  F1  F3G3 F3G3                                               1   F1  0   0  0   F1  F3G3 F3G3                                         XVII  3   F2G1                                                                               0   0  0   0   F1   0                                                  1   0   0   0  0   0   0    0                                            XVIII 3   F2  0   0  0   0   F2G1 F1G1                                               1   0   0   0  0   0   F1   0                                            XIX   3   F2  0   0  F1  F2  F3G2 F3G3                                               1   F1  0   0  0   F1  F2   F3                                           XX    3   0   0   0  0   0   C1   0                                                  1   0   0   0  0   0   0    0                                            XXI   3   F1  0   0  0   0   0    0                                                  1   0   0   0  0   0   0    0                                            XXII  3   F1  0   0  0   0   0    0                                                  1   0   0   0  0   0   0    0                                            XXIII 3   0   0   0  0   0   F1   F1                                                 1   0   0   0  0   0   0    0                                            XXIV  3   0   0   0  0   0   F2   F1                                                 1   0   0   0  0   0   0    0                                            XXV   3   0   0   0  0   0   F1   0                                                  1   0   0   0  0   0   0    0                                            Comments                     more                                                                           tillers                                           __________________________________________________________________________                       Appl'n.                                                                        Rate                                                                               Compound Nos.                                                          Species                                                                            (lb/A)                                                                             4956                                                                               4957                                                                               4958                                                                               4959                                         __________________________________________________________________________                   I   3   F3G3                                                                               F3G3                                                                               F3G3                                                                               F3G3                                                           1   F2G2                                                                               F3G3                                                                               F3G2                                                                               F3G3                                                       II  3   F3G3                                                                               F3G3                                                                               F3G3                                                                               F3G3                                                           1   F2G2                                                                               F3G3                                                                               F3G3                                                                               F3G3                                                       III 3   F1G1                                                                               F2G1                                                                               F2G2                                                                               F2G1                                                           1   0   0   G1F1                                                                               F1                                                         IV  3   G1  F1G1                                                                               F1G1                                                                               G1                                                             1   0   0   0   0                                                          V   3   F2G1                                                                               F2G2                                                                               F3G2                                                                               F2G2                                                           1   0   F1  F2G1                                                                               F1                                                         VI  3   0   0   0   0                                                              1   0   0   0   0                                                          VII 3   F1  F1  F1  F1                                                             1   0   0   F1  0                                                          VIII                                                                               3   F2  F3G1                                                                               F3G2                                                                               F3G2                                                           1   F1  F1  F2  F1                                                         IX  3   F3G2                                                                               F3G3                                                                               F3G3                                                                               F3G3                                                           1   F3  F3G2                                                                               F3G3                                                                               F3G3                                                       X   3   F3G2                                                                               F3G2                                                                               F3G3                                                                               F3G3                                                           1   F2G1                                                                               F2G2                                                                               F3G2                                                                               F2G2                                                       XI  3   F3G3                                                                               F3G3                                                                               F3G3                                                                               F3G2                                                           1   F2G1                                                                               F1G1                                                                               F2G2                                                                               F2G2                                                       XII 3   F2G1                                                                               F3G2                                                                               F3G3                                                                               F3G3                                                           1   F1  F2G1                                                                               F3G2                                                                               F2G2                                                       XIII                                                                               3   F3E3                                                                               F3G3                                                                               F3G3                                                                               F3G3                                                           1   F3#2                                                                               F3E1                                                                               F3E3                                                                               F3E2                                                       XIV 3   F1  F2  F2  F2                                                             1   F1  F1  F2  F2                                                         XV  3   F2G2                                                                               F2G2                                                                               F3G2                                                                               F2G2                                                           1   F2G1                                                                               F2G1                                                                               F3G2                                                                               F2G2                                                       XVI 3   F3G3                                                                               F3G3                                                                               F3G3                                                                               F3G3                                                           1   F3G2                                                                               F3G3                                                                               F3G3                                                                               F3G3                                                       XVII                                                                               3   F1G1                                                                               F1  F2  F1                                                             1   F1  F1  F1  F1                                                         XVIII                                                                              3   F2G1                                                                               F2G2                                                                               F3G2                                                                               F2G1                                                           1   F1  F1  F2  F1                                                         XIX 3   F3G2                                                                               F3G3                                                                               F3G3                                                                               F3G3                                                           1   F3G1                                                                               F3G1                                                                               F2G1                                                                               F2G2                                                       XX  3   F1  F1  F1  F1                                                             1   0   F1 F1                                                                              0                                                              XXI 3   F2  F2  F3G1                                                                               F2                                                             1   F1  F1  F2  F1                                                         XXII                                                                               3   F2  F2  F3G1                                                                               F2                                                             1   F1  F1  F2  F1                                                         XXIII                                                                              3   F1  F1  F2G2                                                                               F1G1                                                           1   0   F1  F1G1                                                                               0                                                          XXIV                                                                               3   F1  F1  F1  F1                                                             1   0   F1  F1  F1                                                         XXV 3   F1  F1  F1  F1                                                             1   0   F1  F1  0                                            __________________________________________________________________________

The use of many of the growth regulator compounds may be demonstrated by treatment of soybeans (Soja max) to increase the number of seed pods and by treating tomato plants (Lycopersicum esculentum) to increase fruit set. In an illustrative experiment, Soja max (Evans variety) and Lycopersicum esculentum (Tiny Tim variety) were grown in 4-inch pots (one plant per pot) filled with greenhouse potting soil (2 parts good top soil, 11/2 parts builders sand, 11/2 parts peat, fertilized with 5 lb. of 12-12-6 fertilizer and 5 lb. of finely ground limestone per cu. yd.). Aqueous spray formulations were prepared and the potted plants were sprayed at a spray volume of 40 gal. per acre and at application rates of 16, 4, 1 and 1/4 oz. per acre. The spray mixtures were prepared by dissolving the proper amount of growth regulator compound in 15 ml. of acetone, adding 2 ml. of a solvent-emulsifier mixture consisting of 60 wt. percent of a commercial polyoxyethylated vegetable oil emulsifier (96 wt. percent active ingredient, Emulphor El-719), 20 wt. percent xylene and 20 wt. percent deodorized kerosene, then bringing total volume up to 80 ml. by addition of a 0.156 wt. percent aqueous solution of liquid non-ionic dispersant (90 wt. percent active trimethylnonyl polyethylene glycol ether, Tergitol TMN-10). Two replicates were sprayed at all application rates. For comparative purposes, plants were also sprayed at 40 gal./acre with water. The number of seed pods and of fruit as percentage of arithmetic mean of the numbers on untreated plants was observed within approximately three weeks after spray treatment and the results are tabulated below. The extent of growth regulatory effect on the plants was estimated on a scale of 0 to 10 and is also recorded in the following table:

                  TABLE 4                                                          ______________________________________                                         GROWTH REGULATING EFFECTS ON TWO SPECIES                                                 TOMATO      SOYBEAN                                                                  G.R.            G.R.                                                           Effect  Fruit   Effect                                         Compound                                                                               Rate    2 Rep.  Increase %                                                                             2 Rep.                                                                               Pod Increase                             No.     oz/A.   Avg.    of Check                                                                               Avg.  % of Check                               ______________________________________                                         4368    16      6.5     150     7.5   203                                              4       4.5     236     4     155                                              1       2.5     192     3     121                                      ______________________________________                                    

The information presented in tabular form herein will enable a worker in the art to make a selection from among the growth regulator compounds of the invention and to make some judgment with regard to application rates, depending upon the effect which is desired. It may be seen, for example, that total kills of some species of vegetation may occur at application rates as high as 5 to 10 lb. per acre, whereas beneficial effects may be observed on living plants at application rates of 1 lb. per acre or less.

The growth regulator compounds are usually applied in combination with inert carriers or diluents, as in aqueous sprays, granules and dust formulations in accordance with established practice in the art. An aqueous spray is usually prepared by mixing a wettable powder or emulsifiable concentrate formulation of a growth regulator with a relatively large amount of water to form a dispersion.

Wettable powders comprise intimate, finely divided mixtures of growth regulator compounds, inert solid carriers and surface active agents. The inert solid carrier is usually chosen from among the attapulgite clays, the kaolin clays, the montmorillonite clays, the diatomaceous earths, finely divided silica and purified silicates. Effective surfactants, which have wetting, penetrating and dispersing ability are usually present in a wettable powder formulation in proportions of from 0.5 to about 10 percent by weight. Among the surface active agents commonly used for this purpose are the sulfonated lignins, naphthalenesulfonates and condensed naphthalenesulfonates, alkylbenzenesulfonates, alkyl sulfates and non-ionic surfactants such as products of condensation of ethylene oxide with alkylphenols.

Emulsifiable concentrates of the growth regulator compounds comprise in each instance, a solution of growth regulator compound in a liquid carrier which is a mixture of water-immiscible solvent and surfactants, including emulsifiers. Useful solvents include aromatic hydrocarbon solvents such as the xylenes, alkylnaphthalenes, petroleum distillates, terpene solvents, ether-alcohols and organic ester solvents. Suitable emulsifiers, dispersing and wetting agents may be selected from the same classes of products which are employed in formulating wettable powders.

In general, the growth regulators are applied in formulations which desirably contain from 0.1 percent to 95 percent of a compound of formula (1) and from 0.1 to 75 percent of a carrier or surfactant. However, direct application to plant seeds prior to planting may be accomplished in some instances by mixing powdered solid growth regulator with seed to obtain a substantially uniform coating which is very thin and comprises only one or two percent by weight or less, based on the weight of the seed. In most instances, however, a nonphytotoxic solvent, such as methanol is employed as a carrier to facilitate the uniform distribution of growth regulator on the surface of the seed.

When a compound is to be applied to the soil, as for a pre-emergence application, granular formulations are sometimes more convenient than sprays. A typical granular formation comprises the growth regulator compound dispersed on an inert carrier such as coarsely ground clay, or clay which has been converted to granules by treatment of a rolling bed of the powdered material with a small amount of liquid in a granulating drum. In the usual process for preparing granular formulations, a solution of the active compound is sprayed on the granules while they are being agitated in a suitable mixing apparatus, after which the granules are dried with a current of air during continued agitation. 

I claim:
 1. The method of regulating the growth of plants comprising applying to the plants, the seed or the soil an effective amount of a compound having one of the following structural formulas; ##STR10## in which R, R¹ and R⁵ are hydrogen or C₁ to C₅ alkyl, R² and R³ are alike or unlike, one of which may be hydrogen but otherwise are substituents selected from branched or unbranched C₁ to C₅ alkyl, alkenyl, alkynyl, C₂ to C₅ hydroxyalkyl or alkoxyalkyl, C₃ to C₅ cycloalkyl, furfuryl, pyridyl, benzyl, phenyl, C₁ to C₅ alkyl-substituted phenyl, or --NR² R³ together may be 2,5-dimethyl-1-pyrryl, 4-morpholinyl, or 1-pyrrolidinyl, R⁴ is halogen, nitro, cyano, trifluoromethyl or C₁ to C₅ alkyl and n is zero, one or two.
 2. The method of regulating the growth of plants comprising applying to the plants, the seed or the soil an effective amount of a compound having one of the following structural formulas: ##STR11## in which R is H, R¹ is CH₃, --NR² R³ is -1-piperidyl, R⁵ is hydrogen or C₁ to C₅ alkyl and n is zero.
 3. The method of regulating the growth of plants comprising applying to the plants, the seed or the soil an effective amount of a compound having one of the following structural formulas: ##STR12## in which R is H, R¹ is CH₃, --NR² R³ is --N(nonyl)₂, R⁵ is hydrogen or C₁ to C₅ alkyl and n is zero.
 4. The method of regulating the growth of plants comprising applying to the plants, the seed or the soil an effective amount of a compound having one of the following structural formulas: ##STR13## in which R is H, R¹ is CH₃, --NR² R³ is --N-methylcyclooctyl, R⁵ is hydrogen or C₁ to C₅ alkyl and n is zero.
 5. The method of regulating the growth of plants comprising applying to the plants, the seed or the soil an effective amount of a compound having one of the following structural formulas: ##STR14## in which R is H, R¹ is CH₃, --NR² R³ is --N(octyl)₂, R⁵ is hydrogen or C₁ to C₅ alkyl and n is zero.
 6. The method of regulating the growth of plants which comprises applying to the plants pre- or post-emergently an effective amount of a composition comprising from 0.1 to 95 weight percent of a compound as specified in claim 1 in combination with a carrier or surface active agent.
 7. The method of increasing fruit set of crop plants which comprises applying to the plant foliage an effective amount of a compound as specified in claim 1 in combination with an inert carrier and a surface active agent.
 8. The method of regulating the growth of plants which comprises applying to the plants, a compound as specified in claim 1 in which the substituents represented by R, R¹,--NR² R³ and (R⁴)n are those tabulated below:

    ______________________________________                                         R     R.sup.1 --NR.sup.2 R.sup.3 (R.sup.4).sub.n                               ______________________________________                                         H     CH.sub.3                                                                               --N(C.sub.2 H.sub.5).sub.2                                                                        n = o                                         H     CH.sub.3                                                                               --N(CH.sub.3).sub.2                                                                               n = o                                         H     CH.sub.3                                                                 4-morpholinyl                                                                        n = o                                                                    H     CH.sub.3                                                                 1-pyrrolidinyl                                                                       n = o                                                                    H     CH.sub.3                                                                               --N--methyl benzyl n = o                                         H     CH.sub.3                                                                               --N--isopropyl benzyl                                                                             n = o                                         H     CH.sub.3                                                                               --N--methyl phenyl n = o                                         H     CH.sub.3                                                                               --N--ethyl phenyl  n = o                                         H     CH.sub.3                                                                               --N--(CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                                           n = o                                         H     CH.sub.3                                                                               --N(isopropyl).sub.2                                                                              n = o                                         H     CH.sub.3                                                                               --N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                                    n = o                                         H     CH.sub.3                                                                               --N--propyl phenyl n = o                                         H     CH.sub.3                                                                               --N(sec. butyl).sub.2                                                                             n = o                                         H     CH.sub.3                                                                               --N(CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3).sub.2                                           n = o                                         H     CH.sub.3                                                                               -- N(allyl).sub.2  n = o                                         H     CH.sub.3                                                                               --N(isobutyl).sub.2                                                                               n = o                                         H     CH.sub.3                                                                               --N--methyl propyl n = o                                         H     CH.sub.3                                                                               --N--propyl isopropyl                                                                             n = o                                         H     CH.sub.3                                                                               --N--propyl isobutyl                                                                              n = o                                         H     CH.sub.3                                                                               --N--propyl sec. butyl                                                                            n = o                                         H     CH.sub.3                                                                               --N--propyl butyl  n = o                                         H     CH.sub.3                                                                               --N--benzyl 2-propenyl                                                                            n = o                                         H     CH.sub.3                                                                               --N--allyl phenyl  n = o                                         H     CH.sub.3                                                                               --N--ethyl p-tolyl n = o                                         H     CH.sub.3                                                                 4-morpholinyl                                                                        3-fluoro                                                                 H     CH.sub.3                                                                               --NH--CH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                         n = o                                         H     CH.sub.3                                                                               --NH--C(CH.sub.3).sub.3                                                                           n = o                                         H     CH.sub.3                                                                               --NH--cyclopropyl  n = o                                         H     CH.sub.3                                                                               --NH--cyclopentyl  n = o                                         H     CH.sub.3                                                                               --N(CH.sub.3) (CH.sub.2 CH.sub.2 OH)                                                              n = o                                         H     CH.sub.3                                                                               --N(CH.sub.3).sub.2                                                                               2,5-dimethyl                                  H     CH.sub.3                                                                               --N(CH.sub.3).sub.2                                                                               4-nitro                                       H     CH.sub.3                                                                               --N(CH.sub.3 ).sub.2                                                                              4-fluoro                                      H     CH.sub.3                                                                               --N(CH.sub.3).sub.2                                                                               4-cyano                                       H     CH.sub.3                                                                               --N(CH.sub.3).sub.2                                                                               4-CF.sub.3                                    H     H       --N(CH.sub.3).sub.2                                                                               3-fluoro                                      H     CH.sub.3                                                                               1-pyrrolidinyl     3-fluoro                                      4-CH.sub.3                                                                           CH.sub.3                                                                               --NHCH.sub.2 CH.sub.2 CH.sub.2 CH.sub.3                                                           n = o                                         H     CH.sub.3                                                                               --NH--CH.sub.2 CH.sub.2 OCH.sub.3                                                                 n = o                                         H     CH.sub.3                                                                               --N--methyl furfuryl                                                                              n = o                                         H     CH.sub.3                                                                 2,5-dimethyl-1-pyrryl                                                                n = o                                                                    H     CH.sub.3                                                                               --NH--2-pyridyl    n = o.                                        ______________________________________                                    


9. The method of claim 7 in which the crop plants are of the species Lycopersicum esculentum.
 10. The method of claim 7 in which the crop plants are of the species Soja max.
 11. The method of regulating the growth of plants comprising applying to the plants, the seed or the soil an effective amount of a compound having one of the following structural formulas: ##STR15## in which R is hydrogen, R¹ is methyl, --NR² R³ is --N(CH₃)₂, (R⁴)_(n) is 3-acetyl, and R⁵ is hydrogen or C₁ to C₅ alkyl. 